CN1289584C - Stabilizer composition, production and use thereof - Google Patents

Abstract

The present invention provides a stabilizer composition comprising at least one onium perchlorate and at least one organic solvent, preferably for halogen-containing polymers.

Description

Stabilizer composition, its preparation method and its use

The present invention relates to a stabilizer composition for halogen-containing polymers, a process for its preparation and its use.

It is well known that halogen-containing plastics are prone to undesired decomposition reactions when exposed to heat during processing or during prolonged use. On decomposition of halogen-containing polymers, especially in the case of PVC, hydrochloric acid is formed, which is released from the polymer strands, whereby colored unsaturated plastics having chromophoric polyolefin sequences are obtained.

A particularly difficult problem arises from the fact that halogen-containing polymers only have the rheological framework conditions necessary for processing at relatively high processing temperatures. However, at such temperatures, unstabilized polymers already begin to undergo significant polymer decomposition, which leads not only to the aforementioned undesirable color changes, but also to changes in material properties. Furthermore, the hydrochloric acid released by unstabilized halogen-containing polymers at such processing temperatures also leads to significant corrosion of processing equipment. This process is particularly effective when production interruptions occur during the processing of such halogen-containing polymers, for example by extrusion, into shaped bodies and the polymer mass remains in the extruder for a relatively long time. During this time, the above-mentioned decomposition reactions may occur, whereby the feed material present in the extruder cannot be used and the extruder may be damaged.

Furthermore, polymers that have undergone such decomposition tend to form sticks on processing equipment, which can only be removed again with difficulty.

To solve the above-mentioned problems, compounds as so-called stabilizers are usually added to the halogen-containing polymers to be processed, which compounds are supposed to prevent the above-mentioned decomposition reactions as far as possible. Generally, such a stabilizer means a solid which is added to the polymer to be processed prior to its processing.

Suitable stabilizers are, for example, perchlorates, wherein perchlorates are generally used according to the prior art as inorganic perchlorates, for example in the form of sodium perchlorate. The problem with these compounds, however, is that they do not meet the requirements set forth for them in all cases.

Furthermore, solid stabilizers often have the disadvantage that they can lead to undesired clouding in the final product, especially in the case of transparent shaped bodies. However, such turbidity limits the acceptability of such end products on the part of users for further processing and prevents their use in fields of application in which the highest possible transparency is critical.

To cope with such problems, there are proposals to use liquid stabilizers such as sodium perchlorate. However, these stabilizers have the disadvantage that their performance in the sense of improving the initial color is still insufficient.

It was therefore the object of the present invention to provide a stabilizer composition which can be used in the production of halogen-containing polymers and leads to an improved initial color. Furthermore, it is the object of the present invention to provide a liquid stabilizer composition which can be used in the production of halogen-containing polymers and in the case of transparent end products, for example made of hard PVC or soft PVC In the case of the final product, reduce turbidity. Furthermore, it is the object of the present invention to provide a stabilizer composition which, compared to the stabilizers known from the prior art, exhibits an improved effect on the initial color when processing halogen-containing polymers.

It has been found that solid and liquid stabilizer compositions containing at least one organo-onium perchlorate solve the above-mentioned tasks.

Therefore, a first subject of the present invention is a stabilizer composition containing one organonium salt of perchloric acid or a mixture of two or more organonium salts of perchloric acid, and at least one organic solvent.

By "stabilizer composition" is meant within the scope of the present invention a composition which can be used to stabilize halogen-containing polymers. To achieve this stabilizing effect, the stabilizer compositions of the invention are generally mixed with a halogen-containing polymer which is to be stabilized and then processed. However, it is likewise possible to admix the stabilizer compositions according to the invention with the halogen-containing polymers to be stabilized during processing.

The so-called concept "liquid" means within the scope of the present invention that the stabilizer composition of the present invention is at least in the temperature range of about 45 to about 100°C, preferably in the temperature range of about 30 to about 120°C, for example at about 15- Agglomerated states in the temperature range of about 150°C, especially in the temperature range of about 0 to about 200°C.

The term "solvent" as used herein refers to a compound which can dissolve one organonium salt of perchloric acid or two or more organonium salts of perchloric acid in an amount of at least 0.1% by weight. mixture.

Compounds referred to in the context of this document as "onium salts" are ammonium, sulfonium or phosphonium salts. "Onium salt" according to the present invention refers to an organic onium salt. This means that the ammonium, sulfonium or phosphonium group of the onium salt bears at least one organic group. The onium salts according to the invention can here, depending on the type of onium radicals, carry 1, 2, 3 or 4 organic radicals. These organic groups can be linked here, for example, via C-X, where X stands for S, N or P, to the onium group. However, these organic groups can likewise be linked to the onium group via other heteroatoms, for example oxygen atoms.

Onium perchlorates usable within the scope of the present invention have at least one positively charged N, P or S atom, or two or more such positively charged N, S or P atoms, or two or Mixtures of more of the above positively charged atom types.

Within the scope of the invention, a compound is used as perchlorate which carries at least one organic group and up to the maximum possible number of organic groups on the N, S or P atom. If the perchlorate oniums usable according to the invention have fewer organic groups than are necessary for the formation of positively charged onium ions, then in the usual manner known to those skilled in the art by means of suitable The acid is protonated to be positively charged, so that in this case the corresponding perchlorate onium bears at least one proton in addition to the organic group.

The compounds used as perchlorates according to the invention can therefore also be compounds which have a positive charge due to the protonation reaction. However, it is likewise possible within the scope of the inventive stabilizer combination to use onium perchlorates, which have a positive charge due to the peralkylation reaction. Examples of such compounds are tetraalkylammonium perchlorates, trialkylsulfonium perchlorates or tetraalkylphosphonium perchlorates. However, it is also provided within the scope of the present invention that the peralkylated onium perchlorates usable according to the invention have aryl, alkaryl, cycloalkyl, alkenyl, alkynyl or cycloalkenyl groups. It is likewise possible and provided according to the invention that the onium salts usable within the scope of the inventive stabilizer composition have two or optionally more different substituent types, for example alkyl and cycloalkyl, or alkyl and Aryl. It is likewise possible and provided within the scope of the present invention that the onium salts usable within the context of the stabilizer composition according to the invention have substituents which themselves are substituted by one or more functional groups. "Functional groups" are referred to herein as groups which improve the action of the stabilizer composition or at least do not impair or only insignificantly impair the action of the stabilizer composition. Corresponding functional groups can be, for example, NH groups, _NH groups, OH groups, SH groups, ester groups, ether groups, thioether groups, isocyanurate groups or ketone groups or mixtures of two or more of the aforementioned groups .

As phosphonium perchlorate within the scope of the invention it is possible in principle to use all compounds which lead to phosphonium perchlorate by corresponding reaction of suitable reactants. The phosphonium perchlorates which can be used according to the invention can be obtained, for example, by corresponding reactions of tetraalkylphosphorus halides, tetracycloalkylphosphorus halides or tetraarylphosphorus halides. Suitable phosphonium perchlorates are thus derived, for example, from tetraalkylphosphonium salts such as tetra-n-ethylphosphonium bromide, tetra-n-propylphosphonium bromide, tetra-n-butylphosphonium bromide, tetra-n-isobutylphosphonium bromide, bromide tetra-n-pentylphosphonium bromide, tetra-n-hexylphosphonium bromide and similar tetraalkylphosphonium salts. Furthermore, the phosphonium perchlorates which are also suitable in principle for use within the scope of the stabilizer composition according to the invention are derived, for example, from tetracycloalkylphosphonium salts or tetraarylphosphonium salts. Suitable phosphonium perchlorates are thus based, for example, on tetracycloalkylphosphonium or tetraarylphosphonium salts, such as tetracyclohexylphosphonium bromide or tetraphenylphosphonium bromide and similar tetracycloalkylphosphonium or tetraarylphosphonium salts Salt. Within the scope of the present invention, the aforementioned compounds may be unsubstituted, but they may also have one or more of the aforementioned substituents, as long as these substituents do not have an adverse effect within the scope of the stabilizer composition of the invention and do not adversely affect affect the purpose of use of the stabilizer composition.

It is also possible within the scope of the invention to use organic phosphonium perchlorates which carry different types of organic substituents on the phosphorus atom, which can optionally be substituted differently.

Within the scope of a preferred embodiment of the invention, tetra-n-butylphosphonium perchlorate or triphenylbenzylphosphonium perchlorate are used as phosphonium perchlorate.

As sulfonium perchlorate it is possible in principle within the scope of the invention to use all compounds which lead to sulfonium perchlorate by corresponding reaction of suitable reactants. The sulfonium perchlorates which can be used according to the invention can be obtained, for example, by corresponding reactions of sulfides such as alkyl monosulfides, alkyl disulfides, dialkylsulfides or polyalkylsulfides. Suitable sulfonium perchlorates are thus derived, for example, from dialkyl sulfides such as ethylbenzyl sulfide, allyl benzyl sulfide, or from alkyl disulfides such as hexane disulfide, heptane disulfide, Octane disulfides and similar alkyl disulfides. Furthermore, sulfonium perchlorates which are also suitable in principle for use within the context of the stabilizer composition according to the invention are derived, for example, from tricycloalkylsulfonium salts or triarylsulfonium salts. Suitable sulfonium perchlorates are thus based, for example, on tricycloalkylsulfonium or triarylsulfonium salts such as tricyclohexylsulfonium bromide or triphenylsulfonium bromide and similar tricycloalkylsulfonium or triarylsulfonium salts. Also suitable are trialkylsulfoxonium salts, triarylsulfoxonium salts or tricycloalkylsulfoxonium salts, such as trimethylsulfoxonium perchlorate. The compounds mentioned above may be unsubstituted within the scope of the present invention, but they may also have one or more of the above-mentioned substituents, as long as these substituents have no adverse effect within the scope of the stabilizer composition of the present invention and do not adversely affect Purpose of use of the stabilizer composition.

It is also possible within the scope of the present invention to use organic sulfonium perchlorates which carry different types of organic substituents on the sulfur atom, which can optionally be substituted differently. Within the scope of a preferred embodiment of the invention, trimethylsulfoxonium perchlorate is used as sulfonium perchlorate.

As ammonium perchlorate it is possible in principle within the scope of the invention to use all compounds which lead to ammonium perchlorate by corresponding reaction of suitable reactants. The ammonium perchlorate usable according to the invention can be obtained, for example, by corresponding reaction of amines or amides such as alkyl monoamines, alkylene diamines, alkyl polyamines, secondary or tertiary amines or dialkylamines . Thus, suitable ammonium perchlorates are derived, for example, from primary mono- or polyamino compounds having 2 to about 40, for example 6 to about 20, carbon atoms. For example ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, substituted amines with 2 to about 20 carbon atoms, such as 2-(N,N-dimethylamino)-1-amino ethane. Suitable diamines have, for example, two primary amino groups, two secondary amino groups, two tertiary amino groups, or one primary and one secondary amino group, or one primary and one tertiary amino group, or one secondary and one tertiary amino group. For example, diaminoethane, isomeric diaminopropane, isomeric diaminobutane, isomeric diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-amine Methyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, amino ethyl ethanolamine, hydrazine, hydrazine hydrate, or triamines such as diethylenetriamine or 1,8-diamino-4-aminomethyloctane, or tertiary amines such as triethylamine, tributylamine, dimethyl Benzylamine, N-ethylmorpholine, N-methylmorpholine, N-cyclohexylmorpholine, dimethylcyclohexylamine, dimorpholinodiethyl ether, 1,4-diazabicyclo [2.2.2] Octane, 1-azabicyclo[3.3.0]octane, N,N,N',N'-tetramethylethylenediamine, N,N,N',N' -Tetramethylbutanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethylether, bis (Dimethylaminopropyl)urea, N,N'-dimethylpiperazine, 1,2-dimethylimidazole or bis(4-N,N-dimethylaminocyclohexyl)methane.

Also suitable are aliphatic aminoalcohols having 2 to about 40, preferably 6 to about 20, carbon atoms, such as triethanolamine, tripropanolamine, tributanolamine, tripentanolamine, 1-amino-3 , 3-Dimethyl-5-pentanol, 2-aminohexane-2',2"-diethanolamine, 1-amino-2,5-dimethylcyclohexane-4-ol, 2-aminopropanol Alcohol, 2-aminobutanol, 3-aminopropanol, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 5-aminopentanol, 3-aminomethyl-3 , 5,5-trimethylcyclohexanol, 1-amino-1-cyclopentane-methanol, 2-amino-2-ethyl-1,3-propanediol, 2-(dimethylaminoethoxy) Ethanol, aromatic-aliphatic or aromatic-cycloaliphatic amino alcohols having 6 to about 20 carbon atoms, in which heterocyclic or carbocyclic ring systems are used as aromatic structure, such as naphthalene derivatives or especially benzene derivatives , such as 2-aminobenzyl alcohol, 3-(hydroxymethyl)aniline, 2-amino-3-phenyl-1-propanol. 2-amino-1-phenylethanol, 2-phenylglycinol or 2-amino-1-phenyl-1,3-propanediol, and mixtures of two or more of the above compounds.

Within the scope of a further embodiment of the invention, as ammonium perchlorate, perchlorate salts of heterocyclic compounds having cyclic amino-bearing ring systems are used.

Use is made here, for example, of the perchlorates of heterocyclic aminoalcohols which have at least 2, preferably at least 3, amino groups in the ring. Trimerization products of isocyanates are particularly suitable as central ring constituents of the ammonium perchlorate which can be used according to the invention.

Suitable here are, for example, hydroxyl-containing isocyanurates of the general formula I:

wherein the group Y and the index m are in each case the same or different, m represents an integer from 0 to 20, Y represents a hydrogen atom or a straight-chain or branched, saturated or unsaturated having 1 to about 10 carbon atoms of alkyl. Particular preference is given within the scope of the invention to using tris(hydroxymethyl)isocyanurate (THEIC) as a component of the stabilizer composition according to the invention. Also suitable as ammonium perchlorate are, for example, compounds in which amino groups attached to substituted aromatic or heteroaromatic systems are present, such as aminobenzoic, aminosalicylic or aminopyridine and their suitable derivative.

Within the scope of a preferred embodiment of the invention, as ammonium perchlorate, 2-ethylcarboxypyridinium perchlorate, formamide perchlorate, tetra-n-butylphosphonium perchlorate, trimethyl perchlorate Sulfoxonium perchlorate, perchlorate of trishydroxyethylisocyanurate, perchlorate of 2-(diethylamino)ethanol, perchlorate-N-(2-hydroxyethyl)morpholinium , or trioctylammonium perchlorate, or a mixture of two or more of the above compounds.

The stabilizer composition according to the invention may, for example, contain only one of the abovementioned onium perchlorates within the scope of the invention. It is likewise possible and provided within the scope of the invention that the stabilizer composition according to the invention contains a mixture of two or more of the aforementioned onium perchlorates. This can be a mixture of two or more different types of onium perchlorate, i.e. for example a mixture of ammonium perchlorate and sulfonium perchlorate, or a mixture of ammonium perchlorate and phosphonium perchlorate, or a mixture of perchlorate A mixture of sulfonium chlorate and phosphonium perchlorate, or a mixture of ammonium perchlorate and sulfonium perchlorate and phosphonium perchlorate. Within the scope of the present invention, the inventive stabilizer composition may also contain a mixture of two or more onium perchlorates of one type, i.e. a mixture of two or more ammonium perchlorates, and two or more More mixtures of sulfonium perchlorates, and mixtures of two or more phosphonium perchlorates.

If the stabilizer composition according to the invention contains a mixture of two or more onium perchlorates, the two or more onium perchlorates can in principle be present in the stabilizer composition according to the invention in any ratio. It is within the scope of the present invention that the stabilizer compositions of the present invention contain from 0.01 to about 30% by weight, for example from about 0.1 to about 20% by weight, based on the total composition, of an organonium salt of perchloric acid or a combination of perchloric acid. A mixture of one or more organonium salts.

Within the scope of the present invention, as organonium salts, the stabilizer compositions according to the invention preferably contain ammonium salts or sulfonium salts or mixtures of two or more such compounds, in particular ammonium salts.

If the stabilizer compositions according to the invention are present in the liquid state, they may have, for example, one or more of the solvents listed below or one or more of the additives described below, in addition to the onium perchlorate.

The stabilizer composition according to the invention contains, in addition to one perchlorate onium or a mixture of two or more perchlorate oniums, at least one organic solvent.

By "solvent" is meant within the scope of the present invention a compound or a mixture of two or more compounds which is liquid within a certain temperature range and capable of dissolving the onium perchlorate present in the composition of the present invention or a mixture of two or more such perchlorate oniums. Suitable solvents within the scope of the present invention are in the temperature range of about 45 to about 100°C, preferably in the temperature range of about 30 to about 120°C, for example in the temperature range of about 15 to about 150°C, especially at about It is liquid in the temperature range of 0 to about 200°C.

Within the scope of a preferred embodiment of the present invention, compounds or mixtures of two or more such compounds which are suitable as plasticizers for halogen-containing polymers are used as solvents.

Compounds suitable as solvents in the sense herein are thus, for example, compounds of the phthalate class, such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, phthalate, Dihexyl phthalate, bis(2-ethylhexyl) phthalate, di-n-octyl phthalate, di-isooctyl phthalate, diisononyl phthalate, phthalate Diisodecyl dicarboxylate, dicyclohexyl phthalate, bis(methylcyclohexyl) phthalate, dimethylethylene glycol phthalate, dibutylethylene phthalate Alcohol esters, benzylbutyl phthalate or diphenyl phthalate, and mixtures of phthalates, for example those having 7-9 carbon atoms or 9-11 carbon atoms in the alcohol of the ester A mixture of alkyl phthalates, or a mixture of alkyl phthalates having 6-10 carbon atoms and 8-10 carbon atoms in the alcohol of the ester. Particularly suitable here in the sense of the invention are dibutyl phthalate, dihexyl phthalate, di(2-ethylhexyl) phthalate, di-n-octyl phthalate, Diisooctyl phthalate, diisononyl phthalate, diisodecyl phthalate, di(isotridecyl) phthalate and benzyl butyl phthalate and the above Mixture of alkyl phthalates.

Also suitable as solvents are esters of aliphatic dicarboxylic acids, especially esters of adipic, azelaic or sebacic acid or mixtures of two or more of the aforementioned compounds. Examples of such solvents are bis(2-ethylhexyl) adipate, diisooctyl adipate, diisononyl adipate, diisodecyl adipate, benzylbutyl adipate, Benzyl octyl dioate, bis(2-ethylhexyl) azelate, bis(2-ethylhexyl) sebacate, and diisodecyl sebacate. In a further embodiment of the invention bis(2-ethylhexyl) acetate and diisooctyl adipate are preferred.

Also suitable as solvents are trimellitic acid esters such as tris(2-ethylhexyl) trimellitate, tris(isotridecyl) trimellitate, triisooctyl trimellitate, and A trimellitate having 6-8, 6-10, 7-9, or 9-11 carbon atoms in the ester group, or a mixture of two or more of the above compounds.

Furthermore, suitable solvents are also, for example, polymeric plasticizers, such as those given in: "Kunststoffadditive (plastic additives)", R.Göchter/H.Müller, Carl Hanser Verlag, 3rd edition, 1989 , Chapter 5.9.6., pp. 342-489, or "PVC Technology (PVC Technology)", W.V.Titow, 4th edition, Elsevier Press, 1984, pp. 165-170. Reference is hereby expressly made to the aforementioned publications and will be cited within the scope of the first mentioned source of information (R.Göchter/H.Müller) and are applicable as plasticizers for use as solvents in the sense of the present invention, especially in Table 9a ( 388-392), 10 (396), 11 (400), 12a (402-404), 13a (408-410), 13b (412), 14 (413 pp), 16 (page 418), 3 (page 479) and 4 (pages 486-488) are considered to form part of the disclosure herein.

The most commonly used raw materials for the preparation of polyester plasticizers are, for example, dicarboxylic acids such as adipic acid, phthalic acid, azelaic acid or sebacic acid, and glycols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol or diethylene glycol or mixtures of two or more of the aforementioned compounds.

Compounds which are also suitable as plasticizers are phosphate esters, see for example "Taschenbuchder Kunststoffadditive (Pocket Handbook of Plastic Additives)", Chapter 5.9.5, pages 408-412. Examples of suitable phosphate esters are tributyl phosphate, tris(2-ethylbutyl) phosphate, tris(2-ethylhexyl) phosphate, tris(chloroethyl) phosphate, (2-ethyl Hexyl) ester diphenyl, triphenyl phosphate, tricresyl phosphate or tris(xylyl) phosphate, or a mixture of two or more of the above compounds.

Particularly suitable as solvents within the scope of the present invention are the compounds listed below: methyl 2-hydroxy-5-methylbenzoate, 2-ethoxybenzyl alcohol, N-ethyl-2,3-di Methylaniline, 2-hydroxy-3-methyl-benzoic acid methyl ester, benzyl laurate, 3,4,5-trimethoxybenzyl alcohol, 3,5-dimethylbenzyl alcohol, 3 -Methylbenzophenone, 2-methoxyacetophenone, 3-cyclohexylpropionic acid, cyclopentanecarboxylic acid, 2,5-dimethylbenzonitrile, 4-(4-methoxyphenyl) -2-butanone, cinnamyl formate, triethyl citrate, dibutyl sebacate, heptaethylene glycol, diethyl sebacate, dibutyl adipate, 1,2-bis(2-acetyl oxy-ethoxy)ethane, diethyl azelate, diethyl corkate, diethyl glutarate, ethyl myristate, dibutyl oxalate, 9-decenyl propionate, Methyl laurate, decyl acetate, butyl cyanoacetate, amyl caproate, nonyl acetate, methyl caprate, methyl nonanoate, undecenyl alcohol, N-methyldioctylamine, di Glycol dibutyl ether, dioctyl ether, 3-decanone, 4-oxa-pimelonitrile, nonanonitrile, diethylene glycol monohexyl ether, diisobutyl ketone, butyl formate, n-tridecane Alcohol, Butyl Methanol, Glutaronitrile, Methyl Propionate, Dimethyl Thioformamide, 1,8-Octylidene Dithiol, 2-Ethyl-1,3-Hexanediol, 4-Decane Alcohol, 1-decanethiol, 1,6-hexylidene dithiol, propylene diiodide, 2-dodecanol, N-butylformamide, diisoamyl sulfide, hexaethylene glycol, pentaethylene glycol , trioctylamine, dipropylene triamine, triethylene glycol, dodecyl mercaptan, 2,2'-dithiodiethylene glycol, diethyl carbonate, m-cresyl isothiocyanate, linolenic acid , triethylenetetramine, 5H-furan-2-one, 4-benzylpiperidine, 1-phenylpiperidine, ethyl isonicotinate, ethyl pyridine-2-carboxylate, 2,3,3- Trimethyl-3H-indole, 3-methylsulfolane, propylene carbonate, 3-piperidinopropionitrile, sulfolane, tetrahydrothiophene-1-oxide, 4-morpholinoethanol, or 4-octyl aniline.

The abovementioned solvents can be present in each case alone or as a mixture of two or more of the abovementioned solvents in the stabilizer composition according to the invention. If the stabilizer composition of the present invention refers to a liquid stabilizer composition, which contains two or more of the above-mentioned compounds as a solvent, one or more of these compounds can be defined in the above definition of the concept "liquid" outside the range provided the total solvent mixture is within the range defined here.

The stabilizer compositions of the present invention contain the solvent or solvent mixture in an amount of about 99.99 to about 2 weight percent, such as about 98 to about 3 weight percent, or about 95 to about 5 weight percent. The solvent content can vary within wide limits, depending on whether the stabilizer composition according to the invention is used as the stabilizer alone or together with one or more additives, or is to be present in solid or liquid state. For example, liquid stabilizer compositions of the present invention, for example, have a solvent content of from about 20 to about 99.99% by weight, or from about 99 to about 30% by weight, or from about 95 to about 35% by weight, or from about 90 to about 40% by weight, Or about 85 to about 50% by weight.

other than one perchlorate, or a mixture of two or more perchlorates, or one perchlorate or a mixture of two or more perchlorates, and a solvent or two or a mixture of more solvents, the stabilizer composition of the present invention may also contain one or more other additives in an amount of up to about 95% by weight, for example up to about 93% by weight or about 91% by weight, or From about 0 to about 90% by weight, or from about 1 to about 85% by weight. The additives referred to here are preferably distributed, preferably dissolved, in the polymer to be stabilized in such a way that the stabilized polymer does not become opaque due to these additives.

The solid stabilizer composition according to the invention is prepared in principle using methods known to the person skilled in the art for mixing different kinds of solid substances or solid and liquid substances, for example by simply mixing onium perchlorate with other additives. Mix and finish.

The preparation of the liquid stabilizer compositions of the present invention is accomplished according to various methods. In principle, to prepare a stabilizer composition according to the invention, it is possible, for example, to dissolve onium perchlorate in a suitable organic solvent.

A subject of the present invention is therefore a process for the preparation of the stabilizer composition according to the invention, in which onium perchlorate is dissolved in an organic solvent.

Since many of the onium perchlorates which can be used within the scope of the process according to the invention and in the stabilizer composition according to the invention are not commercially available and must therefore be prepared by the user themselves, they are suitable for use in the preparation of perchlorate The onium acid process is integrated into the process according to the invention for the preparation of the stabilizer composition of the invention. For this purpose, different implementation methods can be selected, one of which is described below by way of example.

For example, onium perchlorate can in principle first be prepared from an organic compound capable of forming an onium salt or a salt of such a compound by reaction with perchloric acid or a suitable inorganic salt of perchloric acid. This onium perchlorate can subsequently be isolated and dissolved in a corresponding organic solvent. The reaction is preferably carried out in aqueous solution, wherein perchloric acid or a corresponding suitable perchlorate is usually added dropwise as an aqueous solution having a concentration of about 50 to about 70% by weight. As long as the formed perchlorate onium is insoluble in water, it can be separated out as a precipitate by conventional separation methods, such as filtration or centrifugation.

Another subject of the present invention is therefore a process for the preparation of the stabilizer composition according to the invention, in which perchloric acid or an inorganic salt of perchloric acid is added to an organic compound capable of forming an onium salt or to a salt of such a compound, The onium salt of the organic compound formed therein is separated and dissolved in an organic solvent.

If the organic compound used to form the onium salt forms a water-insoluble organic perchlorate, an alkali metal perchlorate, such as sodium perchlorate or potassium perchlorate, which is an inorganic salt of perchloric acid, in aqueous solution Reacts with onium chloride. A water-insoluble organic perchlorate and a water-soluble alkali metal chloride are formed here. The organic perchlorates which are insoluble in water can be isolated by conventional methods and subsequently dissolved in organic solvents. Optionally, water is also removed from the organic perchlorate in an intermediate step.

If the organic compound used to form the onium salt forms a water-soluble organic perchlorate, a compound is used as the inorganic salt of perchloric acid which forms a water-insoluble chloride. This water-insoluble chloride can be isolated by conventional methods. Then, still remove the water in the soluble perchlorate in the usual way.

Within the scope of a further embodiment of the invention, water-soluble organic onium chlorides are used as organic compounds capable of forming onium salts, while silver perchlorate is preferably used as the inorganic salt of perchloric acid. When silver perchlorate is added to water-soluble organic onium chloride in aqueous solution, a precipitate consisting of insoluble silver chloride is formed and an aqueous solution of organic perchlorate is formed. The precipitate is then filtered off and the organic perchlorate present in the aqueous solution is isolated by customary separation methods, for example by removing the water by distillation.

Another subject of the present invention is therefore a process for the preparation of the stabilizer combination according to the invention, in which organic onium chlorides are used as organic compounds capable of forming onium salts, and alkali metal perchloric acid perchloric acid are used as inorganic salts. Chlorates, wherein an aqueous solution of an alkali metal perchlorate is added to an organic onium chloride, whereby a water-insoluble organic perchlorate and an alkali metal chloride are formed, and the water-insoluble organic perchlorate separate from.

However, the preparation of the perchlorate and stabilizer compositions of the present invention is not simply accomplished from aqueous solutions. The corresponding onium perchlorates can likewise be prepared in organic solution.

To this end, aqueous perchloric acid, or an aqueous solution of an inorganic salt of perchloric acid, is added to an organic solution of an organic compound capable of forming an onium salt or a salt of such a compound. Here organic perchlorates are formed which remain in the organic solution. Here, both water-immiscible and water-miscible organic solvents are possible. Water is then removed from the mixture.

Another subject of the present invention is therefore a process for the preparation of the stabilizer composition according to the invention, in which aqueous perchloric acid or perchloric acid is added to an organic solution of an organic compound capable of forming an onium salt or a salt of such a compound. An aqueous solution of an inorganic salt of chloric acid, where a solution of organic perchlorate is formed.

The stabilizer compositions according to the invention can, as can be obtained by way of example from the process described, in principle contain any suitable compounds as solvents. As a special case which should be specifically mentioned here, the stabilizer composition according to the invention may contain, as solvent or as a component of a solvent, a compound which can be used as a base material for the preparation of onium perchlorate, in particular Used as a base material for the preparation of the onium perchlorate contained in the stabilizer composition of the present invention.

In addition to the essential compounds (perchlorate or perchlorate and at least one organic solvent) that have been described above, the stabilizer composition of the present invention may also contain one or more other additives in the above-mentioned amounts.

Listed below are additives within the scope of the present text which are suitable in principle for use in the stabilizer compositions of the invention either alone or as a mixture of two or more compounds.

Aminouracil compounds of the general formula II are suitable as additives within the scope of the invention:

wherein the radicals R and ^R represent in each case independently of each other hydrogen, an optionally substituted linear or branched, saturated or unsaturated aliphatic alkyl group having ¹ to 44 carbon atoms, having 6 - optionally substituted saturated or unsaturated cycloalkyl with 44 carbon atoms, or optionally substituted aryl with 6-44 carbon atoms, or optionally substituted arane with 7-44 carbon atoms group, or group R ¹ represents an optionally substituted acyl group having 2-44 carbon atoms, and group R ³ represents hydrogen, an optionally substituted straight or branched chain, saturated or An unsaturated aliphatic hydrocarbon group, an optionally substituted saturated or unsaturated cycloaliphatic hydrocarbon group having 6-44 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6-44 carbon atoms.

Also generally suitable as additives are compounds having structural units of the general formula III:

wherein n represents a number from 1 to 100,000, the radicals R ^a , R ^b , R ⁴ and R ⁵ represent in each case independently of each other hydrogen, optionally substituted straight-chain or branched chains with 1 to 44 carbon atoms Chain, saturated or unsaturated aliphatic alkyl, optionally substituted saturated or unsaturated cycloalkyl having 6-44 carbon atoms, or optionally substituted aryl having 6-44 carbon atoms, or An optionally substituted aralkyl group with 7-44 carbon atoms, or the group ^R represents an optionally substituted acyl group with ^2-44 carbon atoms, or the groups R and ^R are connected to form an aromatic or Heterocyclic ring systems, and wherein the group ^R represents hydrogen, optionally substituted linear or branched, saturated or unsaturated aliphatic alkyl or alkylene or oxyalkyl or oxygen with 1 to 44 carbon atoms Alkylene or mercaptoalkyl or mercaptoalkylene or aminoalkyl or aminoalkylene, optionally substituted saturated or unsaturated cycloalkyl or cycloalkylene or oxo ring with 6 to 44 carbon atoms Alkyl or oxycycloalkylene or mercaptocycloalkyl or mercaptocycloalkylene or aminocycloalkyl or aminocycloalkylene, optionally substituted aryl or arylene having 6 to 44 carbon atoms, Or have 1-20 O atoms or S atoms and ether groups or thioether groups of O atoms and S atoms, or represent polymers, which are connected to the position by O, S, NH, NR ^a or CH ₂ C (O) The structural units in brackets are connected, or the group ^R6 is connected to the group ^R4 , so that generally an optionally substituted saturated or unsaturated heterocyclic ring system having 4 to 24 carbon atoms is formed.

Within the scope of a preferred embodiment of the invention, as compounds of the general formula I are used compounds based on α,β-unsaturated β-aminocarboxylic acids, in particular based on β-aminocrotonic acid. Particularly suitable here are the corresponding esters or thioesters of aminocarboxylic acids with monohydric or polyhydric alcohols or thiols, where X in the above cases represents O or S, respectively.

If the radical ^R together with X represents an alcohol or thiol group, such a group can be generated, for example, from methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, iso Octyl Alcohol, Isononyl Alcohol, Decyl Alcohol, Lauryl Alcohol, Myristyl Alcohol, Palmityl Alcohol, Stearyl Alcohol, Ethylene Glycol, Propylene Glycol, 1,3-Butanediol, 1,4-Butanediol, 1,6- Hexylene glycol, 1,10-decanediol, diethylene glycol, thiodiethanol, trimethylolpropane, glycerin, tris(2-hydroxymethyl)isocyanurate, triethanolamine, pentaerythritol, bistriol Methylolpropane, diglycerol, sorbitol, mannitol, xylitol, dipentaerythritol and the corresponding thiol derivatives of the aforementioned alcohols.

Within the scope of ^a particularly preferred embodiment of the invention, a compound of the general formula III is used in which R represents a straight-chain alkyl group with 1 to ⁴ carbon atoms, R represents hydrogen, And R ⁶ represents a linear or branched saturated 1-6 valent alkyl or alkylene group with 2-12 carbon atoms, or a linear, branched or cyclic 2-6 valent The ether alcohol group or thioether alcohol group.

Suitable compounds of general formula III include, for example, stearyl β-aminocrotonate, 1,4-butanediol bis(β-aminocrotonate), thio-diethanol-β-aminocrotonate, tris Methylolpropane tris(β-aminocrotonate), pentaerythritol tetrakis(β-aminocrotonate), dipentaerythritol hexa(β-aminocrotonate), and the like. The above compounds may be contained in the stabilizer composition of the present invention alone or as a mixture of two or more compounds.

Also suitable as compounds of the general formula III are, for example, compounds in which the radicals R ^{and R} are linked to form an aromatic or heteroaromatic system, such as aminobenzoic acid, aminosalicylic acid or aminopyridinecarboxylic acid and other suitable derivatives.

Suitable further additives are, for example, compounds with mercapto-functional sp ² -hybridized carbon atoms, carbazole, carbazole derivatives, or 2,4-pyrrolidinediones or 2,4-pyrrolidinediones derivatized things.

As compounds having at least one mercapto-functional sp ² -hybridized carbon atom, suitable in principle within the scope of the invention are all compounds having the structural unit Z=CZ-SH or the structural unit Z ₂ C=S, where these Structural units in both tautomeric forms may be unique compounds. The sp ² hybridized carbon atom can be a constituent of an optionally substituted aliphatic compound or a constituent of an aromatic system. Suitable compound types are, for example, thiocarbamic acid derivatives, thiocarbamates, thiocarboxylic acids, thiobenzoic acid derivatives, thioacetone derivatives, or thiourea or thiourea derivatives.

Within the scope of a further embodiment of the invention, thiourea or thiourea derivatives are used as additives for sp ² hybridized carbon atoms having at least one thiol function.

Also suitable as additives are, for example, epoxy compounds. Examples of such epoxy compounds are epoxidized soybean oil, epoxidized olive oil, epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil, epoxidized corn oil, epoxidized cottonseed oil and glycidol base compound.

Particularly suitable epoxy compounds are described, for example, on pages 3-5 of EP-A 1046668, the disclosure content contained in this document being explicitly referred to and considered as part of the disclosure content here.

Also suitable as additives within the scope of the present invention are 1,3-dicarbonyl compounds, especially β-diketones and β-ketoesters. Also suitable within the scope of the present invention are dicarbonyl compounds of the general formula R'C(O)CHR"-C(O)R'', as described in EP-1046668 on page 5, especially with regard to the group R', R" and R'' are expressly referred to in this document and the disclosure thereof is considered an integral part of the disclosure herein. Particularly suitable here are, for example, acetylacetone, butyrylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-2,4-heptanedione, benzoyl Acetone, Dibenzoylmethane, Lauroylbenzoylmethane, Palmitoylbenzoylmethane, Stearoylbenzoylmethane, Isooctylbenzoylmethane, 5-Hydroxyhexanoylbenzoylmethane, Triphenyl Formylmethane, bis(4-methylbenzoyl)methane, benzoyl-p-chlorobenzoylmethane, bis(2-hydroxybenzoyl)methane, 4-methoxybenzoylbenzoylmethane, Bis(4-methoxybenzoyl)methane, benzoylformylmethane, benzoylacetylphenylmethane, 1-benzoyl-1-acetylnonane, stearoyl-4-methoxy phenylbenzoylmethane, bis(4-tert-butylbenzoyl)methane, benzoylphenylacetylmethane, bis(cyclohexanoyl)methane, dipivaloylmethane, 2-acetylcyclopentanone, 2-Benzoylcyclopentanone, methyl, ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl diacetoacetate, and propane having 1 to 18 carbon atoms Acetoacetates or butyroacetates, and ethyl, propyl, butyl, hexyl or octyl stearoyl acetates, or polynuclear β-ketoesters, e.g. see EP-A 433230, expressly referred to therein , or dehydroacetic acid and its zinc salt, magnesium salt or alkali metal salt, or the alkali metal chelate, alkaline earth metal chelate or zinc chelate of the above-mentioned compounds, as long as these compounds exist and are soluble in the present invention. agent compositions, or are miscible with such compositions, to achieve the results described above.

The 1,3-diketone compound may be present in the stabilizer composition of the present invention in an amount up to about 20% by weight, for example up to about 10% by weight.

Furthermore, compounds which are suitable as additives within the scope of the stabilizer composition according to the invention are also polyols. Suitable polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, ditrimethylolpropane, inositol, polyvinyl alcohol, ditrimethylolethane, trimethylolpropane, sorbitol, maltitol, isomaltose Alcohol, Lactitol, Lycasin (Maltitol), Mannitol, Lactose, Leuconostoc, Tris (Hydroxymethyl) Isocyanurate, Palatinit (Isomalt), Tetramethylol Cyclohexanol, Tetramethylol cyclopentanol, tetramethylol cycloheptanol, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1-O-α-D-glucopyranosyl (Glycopyranosyl)-D-mannose alcohol dihydrate.

Polyols suitable as additives may be present in the stabilizer composition of the present invention in an amount up to about 30% by weight, for example up to about 10% by weight.

Also suitable as additives are, for example, sterically hindered amines, such as those mentioned on pages 7-27 of EP-A 1046668. With express reference to the sterically hindered amines disclosed in this document, the compounds mentioned therein are considered to form part of the disclosure.

Sterically hindered amines suitable as additives may be present in the stabilizer compositions of the present invention in an amount up to about 30% by weight, for example up to about 10% by weight.

Furthermore, the stabilizer composition of the present invention may also contain an organotin compound or a mixture of two or more organotin compounds as an additive. Suitable organotin compounds are, for example, methyltin tris(isooctylthioglycolate), methyltin tris(isooctyl-3-mercaptopropionate), methyltin tris(isodecylthioglycolate), Dimethyltin bis(isooctylthioglycolate), Dibutyltin bis(isooctylthioglycolate), Monobutyltin tris(isooctylthioglycolate), Bis(isooctylthioglycolate) dioctyltin tris(isooctylthioglycolate), monooctyltin tris(isooctylthioglycolate) or dimethyltin bis(2-ethylhexyl-β-mercaptopropionate).

Furthermore, the organotin compounds mentioned in EP-A 0742259 on pages 18-29 and described in the process for their preparation can also be used within the scope of the stabilizer compositions according to the invention. The above disclosure is expressly referred to, wherein the compounds mentioned in this document and the processes for their preparation are also considered to be part of the disclosure herein.

The stabilizer composition of the present invention may contain the aforementioned organotin compounds in an amount of up to about 40% by weight, especially up to about 20% by weight.

Within the scope of a further embodiment of the invention, the stabilizer composition according to the invention may contain organic phosphites having 1 to 3 identical, pairwise identical or different organic groups. Suitable organic groups are, for example, linear or branched, saturated or unsaturated alkyl groups having 1 to 24 carbon atoms, optionally substituted alkyl groups having 6 to 20 carbon atoms, or alkyl groups having 7 to 20 An optionally substituted aralkyl group of carbon atoms. Examples of suitable organic phosphites are tris(nonylphenyl) phosphite, trilauryl phosphite, tributyl phosphite, trioctyl phosphite, tridecyl phosphite, phosphorous acid Tris(dodecyl) ester, triphenyl phosphite, diphenyl octyl phosphite, dioctyl phenyl phosphite, tris(octylphenyl) phosphite, tris phosphite Benzyl ester, butyl phosphite xylyl ester, octyl phosphite bis(octylphenyl) ester, tris(2-ethylhexyl) phosphite, tricresyl phosphite, tris(octylphenyl) phosphite 2-cyclohexylphenyl) ester, tris (α-naphthyl) phosphite, tris (phenylphenyl) phosphite, tris (2-phenylethyl) phosphite, tris (dimethyl phosphite) phenyl) ester, tricresyl phosphite or tris(p-nonylphenyl) phosphite or tristearyl sorbitan triphosphite or a mixture of two or more of the above compounds.

The stabilizer composition of the present invention may contain the aforementioned phosphite compounds in an amount of up to about 30% by weight, in particular up to about 10% by weight.

Furthermore, the stabilizer compositions according to the invention may also contain blocked mercaptans as additives, such as the mercaptans mentioned in EP-A 0742259 on pages 4-18. The disclosure content of the documents given here is explicitly referred to and is also considered to be part of the disclosure content of the present invention.

The stabilizer composition according to the invention may contain the aforementioned blocked mercaptans in an amount of up to about 30% by weight, in particular up to about 10% by weight.

In addition, the stabilizer composition according to the invention may also contain lubricants such as montan waxes, fatty acid esters, purified or hydrogenated natural or synthetic triglycerides or partial esters, polyethylene waxes, amide waxes, chlorinated paraffins, glycerol Esters or alkaline earth metal soaps, as long as these lubricants do not fall within the scope of the concept "solvent" in the sense herein. Furthermore, lubricants which can be used as additives are also described in "Plastic Additives", R. Göchter/H. Müller, Carl Hanser Verlag, 3rd edition, 1989, pp. 478-488. Also suitable as additives are, for example, aliphatic ketones, as described in DE 4204887, and silicon-based lubricants, such as those mentioned in EP-A 0259783, or combinations of the abovementioned compounds, as described in EP-A 0259783 and combination. The aforementioned documents are expressly referred to here, the disclosure therein relating to lubricants being considered as part of the disclosure of this text.

The stabilizer composition according to the invention may contain the aforementioned lubricants in an amount of up to about 70% by weight, in particular up to about 40% by weight.

Compounds which are also suitable as additives for the stabilizer compositions according to the invention are also organic plasticizers, as long as these do not already fall within the scope of the term "solvent" in the sense herein.

Compounds suitable as corresponding plasticizers are, for example, the phthalates mentioned above in the context of the description of solvents, such as dimethyl phthalate, diethyl phthalate, phthalate, Dibutyl phthalate, dihexyl phthalate, bis(2-ethylhexyl) phthalate, di-n-octyl phthalate, di-isooctyl phthalate, di-phthalate Diisononyl formate, Diisodecyl phthalate, Dicyclohexyl phthalate, Di(methylcyclohexyl) phthalate, Dimethylethylene glycol phthalate, Ortho Dibutylethylene glycol phthalate, benzylbutyl phthalate or diphenyl phthalate, and mixtures of phthalates, e.g. with 7-9 carbon atoms in the alcohol of the ester Or a mixture of alkyl phthalates with 9-11 carbon atoms, or a mixture of alkyl phthalates with 6-10 carbon atoms and 8-10 carbon atoms in the alcohol of the ester. Suitable here in particular in the sense of the invention are dibutyl phthalate, dihexyl phthalate, di(2-ethylhexyl) phthalate, di-n-octyl phthalate , diisooctyl phthalate, diisononyl phthalate, diisodecyl phthalate, di(isotridecyl) phthalate and benzyl butyl phthalate, and the aforementioned mixtures of alkyl phthalates.

Also suitable as plasticizers are esters of aliphatic dicarboxylic acids, especially esters of adipic acid, azelaic acid or sebacic acid, or mixtures of two or more of the aforementioned esters. Examples of such plasticizers are bis(2-ethylhexyl) adipate, diisooctyl adipate, diisononyl adipate, diisodecyl adipate, benzylbutyl adipate , benzyl octyl adipate, di(2-ethylhexyl) azelate, bis(2-ethylhexyl) sebacate and diisodecyl sebacate. Preference is given within the scope of a further embodiment of the invention to di(2-ethylhexyl) acetate and diisooctyl adipate.

Also suitable as plasticizers are trimellitates such as tris(2-ethylhexyl) trimellitate, tris(isotridecyl) trimellitate, triisotrimellitate Octyl esters, and trimellitates having 6-8 carbon atoms, having 6-10 carbon atoms, having 7-9 carbon atoms or having 9-11 carbon atoms in the ester group, or both or Mixtures of more of the above compounds.

Furthermore, suitable plasticizers are, for example, polymeric plasticizers, such as those given in: "Plastic Additives", R.Göchter/H.Müller, Carl Hanser Verlag, 3rd edition, 1989, Chapter 5.9.6, pp. 412-415, or "PVC Technology", W.V. Titow, 4th ed., Elsevier Press, 1984, pp. 165-170. The most commonly used raw materials for the preparation of polyester plasticizers are, for example, dicarboxylic acids such as adipic acid, phthalic acid, azelaic acid or sebacic acid, and dihydric alcohols such as 1,2-propanediol, 1, 3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol or diethylene glycol or mixtures of two or more of the abovementioned compounds.

Also suitable as plasticizers are phosphate esters, see for example "The Pocket Handbook of Plastic Additives", chapter 5.9.5, pages 408-412. Examples of suitable phosphate esters are tributyl phosphate, tris(2-ethylbutyl) phosphate, tris(2-ethylhexyl) phosphate, tris(chloroethyl) phosphate, (2-ethyl Hexyl) ester diphenyl, triphenyl phosphate, tricresyl phosphate or tris(xylyl) phosphate, or a mixture of two or more of the foregoing phosphates.

Furthermore, compounds suitable as plasticizers are also chlorinated hydrocarbons (paraffins) or hydrocarbons described in: "Plastic Additives", R. Göchter/H. Müller, Carl Hanser Verlag, 3rd edition, 1989 , Chapter 5.9.14.2, pages 422-425, and Chapter 5.9.14.1, page 422.

The stabilizer composition of the present invention may contain said plasticizer in an amount of up to about 99.5% by weight, especially up to about 30% by weight, up to about 20% by weight, or up to about 10% by weight. Within the scope of preferred embodiments of the present invention, the lower limit of the plasticizer as a component of the stabilizer composition of the present invention is above about 0.1% by weight, for example about 0.5%, 1%, 2% or 5% by weight %.

Within the scope of a further embodiment of the invention, the inventive stabilizer composition may contain antioxidants, UV absorbers or anti-photoaging agents. Suitable antioxidants are described, for example, in EP-A 1046668 on pages 33-35. Suitable UV absorbers and anti-photoaging agents are mentioned in this document on pages 35-36. These two parts of the disclosure are explicitly referred to here and are hereby considered to form an integral part of this text.

The stabilizer composition of the present invention may contain, in addition to the polymer and the stabilizer composition of the present invention, other additives which are insoluble in the stabilizer composition of the present invention. In principle all additives are suitable, for example those which do not affect or do not significantly affect the transparency of polymer compositions produced with the aid of such a stabilizer composition.

In addition, substances suitable as additives in the stabilizer composition of the present invention are hydrotalcite, hydrocalumite, zeolites and alkali metal aluminum carbonates. Suitable hydrotalcites, hydrocalumite, zeolites and alkali aluminum carbonates are described, for example, on pages 27-29 in EP-A1046668, pages 3, 5 and 7 in EP-A256872, in DE-C4106411 Pages 2 and 3, or pages 2 and 3 in DE-C4106404, or DE-C 19860798. These publications are expressly referred to and their disclosures are considered to form part of the disclosure herein.

Hydrotalcites, hydrocalumite, zeolites and alkali metal aluminocarbonates suitable as additives may be present in the stabilizer compositions of the present invention at levels up to about 50% by weight, for example from 0 to about 30% by weight.

Also suitable as additives in the stabilizer compositions of the present invention are metal oxides, metal hydroxides and saturated, unsaturated linear or branched aromatic compounds having preferably from about 2 to about 22 carbon atoms. , metal soaps of cycloaliphatic or aliphatic carboxylic acids or hydroxycarboxylic acids.

As metal cations, metal oxides, metal hydroxides or metal soaps suitable as additives preferably have divalent cations, particularly suitable are cations of calcium or zinc or mixtures thereof.

Examples of suitable carboxylic acid anions include the anions of the following monovalent carboxylic acids: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, Acid, Undecanoic Acid, Dodecanoic Acid, Tridecanoic Acid, Myristic Acid, Palmitic Acid, Lauric Acid, Isostearic Acid, Stearic Acid, 12-Hydroxystearic Acid, 9,10-Dihydroxystearic Acid Fatty acid, oleic acid, 3,6-dioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid , 3,5-di-tert-butyl-4-hydroxybenzoic acid, methylbenzoic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, Sorbic acid, anion of the following divalent carboxylic acids or their monoesters: oxalic acid, malonic acid, maleic acid, tartaric acid, cinnamic acid, mandelic acid, malic acid, glycolic acid, oxalic acid, salicylic acid, having a degree of polymerization of about Polyglycol dicarboxylic acids of 10 to about 12, phthalic, isophthalic, terephthalic or hydroxyphthalic acids, the following trivalent or tetravalent carboxylic acids or their mono-, diesters or tri- Anions of esters: trimellitic acid, trimellitic acid, pyromellitic acid or citric acid, and also the so-called overbased carboxylates, as described, for example, in DE-A4106404 or DE-A4002988 , the disclosure content of the last-mentioned document is hereby considered to be an integral part of the disclosure content of this document.

Within the scope of a preferred embodiment of the present invention, metal soaps are preferably used, the anions of which are derived from saturated or unsaturated carboxylic or hydroxycarboxylic acids having from about 8 to about 20 carbon atoms. Particular preference is given here to calcium or zinc stearate, oleate, laurate, palmitate, behenate, Versatate, hydroxystearate, dihydroxystearate, p-tert-butyl benzoate or (iso)octoate, or a mixture of two or more of the aforementioned salts. Within the scope of a further preferred embodiment of the invention, the polymer composition according to the invention has calcium stearate or zinc stearate or mixtures thereof.

The stabilizer compositions of the present invention may contain the abovementioned metal oxides, metal hydroxides or metal soaps or mixtures of two or more such compounds in amounts of up to about 50% by weight, for example up to about 30% by weight . The stabilizer composition of the present invention may also contain fillers, such as described in "Handbook of PVC Formulating (PVC formulation design manual)", E.J.Wickson, John Wiley & Son s, Inc., 1993, pages 393-449, or reinforcing agents , as described in "The Pocket Handbook of Plastic Additives", R.Gchter/H.Müller, Carl Hanser Verlag, 1990, pp. 549-615, or pigments.

In addition, the stabilizer composition of the present invention may also contain impact modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, optical brighteners, flame retardants, and anti-fog compound. Suitable compounds of these compound types are described, for example, in "Plastic Additives", R. Keβler/H.Müller, Carl Hanser Verlag, 3rd edition, 1989, and in "PVC Formulation Handbook", E.J.Wilson, J.Wiley & Sons , 1993.

Within the scope of the present invention it has been shown that onium salts of perchloric acid are suitable for stabilizing halogen-containing organic polymers. Accordingly, the present invention provides a polymer composition comprising at least a halogen-containing organic polymer and an onium salt of perchloric acid. The amount of onium salt used corresponds to the amount described in the context of the rest of the description for the stabilizer composition of the invention.

Examples of such halogen-containing organic polymers are polymers of vinyl chloride, vinyl resins containing vinyl chloride units in the polymer backbone, copolymerization of vinyl chloride with vinyl esters of aliphatic acids (in particular vinyl acetate) compounds, copolymers of vinyl chloride with esters of acrylic and methacrylic acid or acrylonitrile or mixtures of two or more of the above compounds, copolymers of vinyl chloride with diene compounds or unsaturated dicarboxylic acids or their anhydrides, For example, copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated vinyl chloride polymers and copolymers, vinyl chloride and vinylidene chloride with unsaturated aldehydes, Copolymers of ketones and other compounds such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether, etc., polymers of vinylidene chloride and vinyl chloride and other polymerizable Copolymers of compounds such as those already mentioned above, polymers of chlorovinyl acetate and dichlorodivinyl ether, polymers of chlorinated vinyl acetate, chlorinated acrylic acid and α-substituted Polymers of esters of acrylic acid, chlorinated polystyrenes such as polydichlorostyrene, chlorinated vinyl polymers, polymers of chlorobutadiene and post-chlorinated polymers and their copolymers with vinyl chloride And mixtures of two or more of the above polymers, or polymer mixtures containing one or more of the above polymers.

Also suitable polymers for stabilization with the stabilizer compositions according to the invention are graft polymers of PVC with EVA, ABS or MBS. Furthermore, preferred base polymers for such graft copolymers are the abovementioned homopolymers and copolymers, especially mixtures of vinyl chloride homopolymers with other thermoplastic or elastomeric polymers, especially with ABS, MBS, NBR , SAN, EVA, CPE; blends of MBAS, PAA (polyalkylacrylate), PAMA (polyalkylmethacrylate), EPDM, polyamide or polylactone.

Polymers which are also suitable for stabilization with the stabilizer compositions according to the invention are also mixtures of halogenated and non-halogenated polymers, for example mixtures of the abovementioned non-halogenated polymers with PVC, in particular mixtures of polyurethanes with PVC.

Furthermore, regrinds of chlorine-containing polymers can also be stabilized with the stabilizer composition according to the invention, and here in principle all regrinds of halogenated polymers mentioned above are suitable. Suitable within the scope of the present invention are, for example, PVC regrinds.

A further subject of the invention therefore relates to a polymer composition comprising at least a halogenated polymer and a stabilizer composition according to the invention.

Within the scope of a preferred embodiment of the invention, the polymer compositions of the invention contain the stabilizer compositions of the invention in amounts of 0.1 to 20 phr, in particular about 0.5 to about 15 phr, or about 1 to about 12 phr. The unit phr means "parts per 100 resins" and thus relates to parts by weight per 100 parts by weight of polymer.

The polymer composition of the present invention preferably contains at least a portion of PVC as a halogenated polymer, wherein the PVC content is in particular at least about 20% by weight, preferably at least about 50% by weight, such as at least about 80% by weight, or at least about 90% by weight. weight%.

The invention also relates to a method for stabilizing a halogen-containing polymer, wherein the halogen-containing polymer, or a mixture of two or more halogen-containing polymers, or one or more halogen-containing polymers A mixture of a compound and one or more halogen-free polymers is mixed with the stabilizer composition of the present invention.

The mixing of the polymers or of the polymers with the stabilizer composition according to the invention can in principle take place at any point before or during the polymerization process. For example, the stabilizer composition can be admixed to polymers present in powder or granular form prior to processing. However, it is likewise possible to add the stabilizer composition to the polymer or polymers in the softened or molten state, for example during processing in an extruder.

The polymer composition according to the invention can be brought into a desired form in a known manner. Suitable methods are, for example, calendering, extrusion, injection molding, sintering, extrusion blow molding or plastisol methods. The polymer compositions according to the invention can also be used, for example, for the production of foams. In principle, the polymer compositions of the invention are suitable for the production of hard PVC or especially soft PVC. The polymer compositions of the invention can be processed into shaped bodies. The invention therefore also provides shaped bodies which contain at least the stabilizer composition of the invention or the polymer composition of the invention.

Within the scope of the present invention, the term "shaped body" includes in principle all three-dimensional bodies which can be produced from the polymer compositions according to the invention. The term "molded body" includes within the scope of the present invention, for example, wire coverings, automotive components, such as those used in the interior of a vehicle, in the engine compartment or on the exterior, cable insulation, decorative films, agricultural films, hoses , sealing profile, office film, hollow body (bottle), packaging film (deep drawn film), blown film, pipe, foam material, heavy profile (window frame), light blocking wall profile, building profile, Wall panels, joints, boards, foam boards, coextrusions with recycled core and shell for electrical equipment or machines such as computers or household appliances. Further examples of shaped bodies which can be produced from the polymer compositions according to the invention are artificial leather, floor coverings, textile coatings, wall papers, coil coatings or underbody protection for motor vehicles.

The present invention also provides the stabilizer composition by one of claims 1-3, or the stabilizer composition prepared by one of claims 4-8, or the polymer composition by one of claim 9 or 10, in Use for the production of polymer moldings or surface coating agents.

The present invention is further set forth below by embodiment.

Preparation of perchlorate onium salt:

Example 1:

15.11 g of nicotinic acid ethyl ester (2-ethylcarboxypyridine) was suspended in 100 ml of water, and 16.73 g of 60% HClO ₄ aqueous solution was added thereto by dropwise addition. After stirring for 20 minutes, a clear solution had formed. After removing the water under vacuum, crystalline 2-ethylcarboxypyridinium perchlorate was obtained. For further testing, the product was used as a 10% (based on perchlorate) solution in propylene carbonate.

Example 2:

To a solution of 4.5 g of formamide in 100 ml of water, 16.73 g of 60% aqueous HClO ₄ was added dropwise with stirring. After 20 minutes of reaction, the water was removed in vacuo. Here, crystalline formamide perchlorate is obtained. For further testing, it was used as a 10% (perchlorate based) solution in formamide.

Example 3:

To a solution of 3.39 g of tetra-n-butylphosphine bromide in 50 ml of water, 1.6 g of 60% by weight HClO ₄ were slowly added dropwise under vigorous stirring. After a few minutes, the formation of a crystalline precipitate was observed. After filtering off, 3.55 g of tetra-n-butylphosphonium perchlorate were isolated. For the further reaction, the product was used as a 10% (based on perchlorate) solution in dioctylphthalate (DOP).

Example 4:

22 g of trimethylsulfoxonium iodide were dissolved in 300 ml of water at room temperature. To this solution was slowly added dropwise 16.74 g of HClO ₄ (60%) with stirring. Trimethylsulfoxonium perchlorate can be isolated quantitatively by careful vacuum evaporation. A solution in DOP (10% based on perchlorate) was further used.

Example 5:

Under stirring, to a solution of 26.05 g of trishydroxyethylisocyanurate in dibutyl oxalate, 16.66 g of 60% HClO ₄ aqueous solution was added dropwise. The resulting 10% solution was dehydrated under vacuum and used in further experiments as obtained.

Embodiment 6:

To a suspension of 11.72 g of 2-(diethylamino)ethanol in water, 16.73 g of 60% _HClO4 in water were added dropwise with stirring. The corresponding perchlorate was isolated quantitatively by evaporation under vacuum. The resulting product was used as a 10% perchlorate-based solution in epoxidized soybean oil.

Example 7a:

To a solution of 13.12 g of N-(2-hydroxyethyl)morpholine in 100 ml of water was added dropwise 16.73 g of 60% aqueous HClO ₄ under stirring. The corresponding -N-(2-hydroxyethyl)morpholinium perchlorate was obtained quantitatively by removing the water under vacuum. Further, a 10% solution based on perchlorate was obtained by dissolving 2.3 g of the obtained product in N-(2-hydroxyethyl)morpholine. This solution was used in further experiments.

Example 7b:

To 45 g of N-(2-hydroxyethyl)morpholine, 8.37 g of 60% HClO ₄ aqueous solution was added dropwise with stirring. The corresponding perchlorate-N-(2-hydroxyethyl)morpholinium was quantitatively obtained by removal of water in vacuo and was used as a 10% solution in N-(2-hydroxyethyl)morpholine in a further used in the test.

Example 8a:

To a solution of 35.36 g of trioctylamine in 100 ml of water, 16.73 g of 60% HClO ₄ aqueous solution was added dropwise with stirring. The corresponding trioctylammonium perchlorate was obtained quantitatively by removing the water in vacuo. Further, a 10% solution based on perchlorate was obtained by dissolving 4.5 g of the obtained product in DOP. This solution was used in further experiments.

Example 8b:

To a mixture of 17.68 g of trioctylamine and 27.5 g of DOP, 8.37 g of 60% aqueous HClO ₄ was added dropwise with stirring. The corresponding trioctylammonium perchlorate was obtained quantitatively by removing the water in vacuo and was used in further experiments as a 10% solution in DOP.

Table 1: components Product name/common name V1 V2 V3 E1 E2 E3 E4 E5 pvc 100 100 100 100 100 100 100 100 plasticizer DOP 60 60 60 60 60 60 60 60 Epoxidized soybean oil 3 3 3 3 3 3 3 3 acid scavengers Calcium hydroxide 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Calcium stearate BS Ceasit SW 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Butylene Glycol Diaminocrotonate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 costabilizer Mercaptobenzimidazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Costabilizer with perchlorate, solid 0.15 Costabilizer containing perchlorate, liquid commercially available Mark CE 530 0.05 According to embodiment 1 (the present invention) 0.15 According to embodiment 2 (the present invention) 0.15 According to embodiment 4 (the present invention) 0.15 According to embodiment 5 (the present invention) 0.15 According to Example 7b (the invention) 0.15 transparency 1 3 1 1 1 1 1 1 HCl stability (DIN VDE 0472 part 614) 25 41 42 37 43 45 44 45 initial color a value -0.7 -0.8 -0.1 -0.9 -1.2 -1.4 -0.9 -0.9 initial color b value 3.3 3.7 4 6.7 5.2 4.2 4.3 3.4 Initial color L value 91.7 91.1 92.6 91 91.3 94.6 94.8 93.3 Color after 15 minutes at 200°C, a value 29.9 3 1.7 -2.9 -4.5 -4.9 -3.2 -4.8 Color after 15 minutes at 200°C, b value 67.3 58.7 62.3 46 36.9 41.9 47.8 40.5 Color after 15 minutes at 200°C, L value 60.4 80.6 81.2 89.3 92.1 90 88.8 90.6

Table 2: components Product name/common name V4 V5 V6 E6 E7 E8 E9 pvc 100 100 100 100 100 100 100 filler chalk 2 2 2 2 2 2 2 Hydrocalumite BS EX 3061 0.6 0.6 0.6 0.6 0.6 0.6 0.6 acid scavengers Calcium hydroxide 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Calcium stearate 0.6 0.6 0.6 0.6 0.6 0.6 0.6 paraffin BL LKT 0.6 0.6 0.6 0.6 0.6 0.6 0.6 polyethylene wax BL PA 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Oxidized polyethylene wax BL PA Spezial 0.1 0.1 0.1 0.1 0.1 0.1 0.1 costabilizer Butylene Glycol Diaminocrotonate 0.3 0.3 0.3 0.3 0.3 0.3 0.3 pigment Titanium dioxide 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Costabilizer with NaClO ₄ , solid 0.2 Costabilizer containing perchlorate, liquid commercially available (NaClO ₄ ) Mark CE 530 0.06 According to Example 7a 0.2 According to Example 7b 0.2 According to Example 8a 0.2 According to Example 8b 0.2 HCl stability (DIN VDE 0472 part 614) twenty two twenty one twenty two twenty two twenty two twenty two twenty two initial color a value -0.4 -0.1 0.7 -3.3 -3.3 -2.7 -2.7 initial color b value 33.6 38.2 39.5 27.8 27.8 28.5 28.6 Initial color L value 81.2 79.5 80.5 83.3 83.5 83 83.2 Color after 15 minutes at 200°C, a value 27.3 25.9 18.1 -0.9 -0.5 -0.1 1.3 Color after 15 minutes at 200°C, b value 43.2 50 56 40.3 40.8 46 47.3 Color after 15 minutes at 200°C, L value 54.7 59.3 69.7 86.2 85.9 85.1 84.2

Claims (13)

1. stabiliser composition that is used for halogen-containing polymer stabilising, it is characterized in that, it contains the organic  salt of a kind of perchloric acid of at least 0.05 weight % or the mixture of the organic  salt of two or more perchloric acid, with at least a organic solvent, described organic solvent is liquid in 0-200 ℃ temperature range.

2. according to the stabiliser composition of claim 1, it is characterized in that it contains the organic  salt of a kind of perchloric acid of 0.1-20 weight % or the mixture of the organic  salt of two or more perchloric acid, based on total composition.

3. according to the stabiliser composition of claim 1 or 2, it is characterized in that its organic  salt that contains is the mixture of ammonium salt or sulfonium salt or  salt or two or more these type of salt.

4. a method for preparing according to the stabiliser composition of one of claim 1-3 wherein is dissolved in perchloric acid  in a kind of organic solvent, and described organic solvent is liquid in 0-200 ℃ temperature range.

5. method for preparing according to the stabiliser composition of one of claim 1-3, the inorganic salt that wherein in the salt of the organic compound that can generate  salt or such compound, add perchloric acid or perchloric acid, to separate out at the  salt of the organic compound of this generation and be dissolved in the organic solvent, described organic solvent be liquid in 0-200 ℃ temperature range.

6. according to the method for claim 5, it is characterized in that, as the organic compound that can generate  salt, use water miscible organic chloride , and, use silver perchlorate as the inorganic salt of perchloric acid, wherein in the water-soluble organic chloride  in the aqueous solution, add silver perchlorate, and form the aqueous solution of precipitation and a kind of organic perchloric acid  thus, the sedimentation and filtration of formation is come out and isolate the organic perchloric acid  that is present in the aqueous solution.

7. according to the method for claim 5, wherein as the organic compound that can generate  salt, use organic chloride , and as the inorganic salt of perchloric acid, use alkaline metal perchlorate, wherein in organic chloride , add the aqueous solution of alkaline metal perchlorate, form water-insoluble organic perchloric acid  and alkali metal chloride thus, and water-insoluble organic perchloric acid  is separated.

8. method for preparing according to the stabiliser composition of one of claim 1-3, wherein in the organic solution of salt in organic solvent of the organic compound that can generate  salt or such compound, the aqueous solution that adds the inorganic salt of aqueous perchloric acid or perchloric acid, described organic solvent is liquid in 0-200 ℃ temperature range, form the solution of organic perchloric acid  in organic solvent at this, this organic solvent is liquid in 0-200 ℃ temperature range.

9. polymer composition, it contains halogen-containing organic polymer and at least according to the stabiliser composition of one of claim 1-3 or according to the stabiliser composition of one of claim 4-8 preparation.

10. according to the polymer composition of claim 9, it is characterized in that its quantity that contains stabiliser composition is 0.1-10 weight %.

11. according to the stabiliser composition of one of claim 1-3 or according to the stabiliser composition of one of claim 4-8 preparation or according to the polymer composition of one of claim 9 or 10 in the purposes aspect preparation polymer moulded bodies or the surface-coated agent.

12. method with halogen-containing polymer stabilising, wherein with a kind of halogen-containing polymkeric substance, or two or more halogen-containing mixture of polymers, or the mixture of polymers of one or more halogen-containing polymkeric substance and one or more halogen, and mix according to the stabiliser composition of one of claim 1-3 or according to the stabiliser composition of one of claim 4-8 preparation.

13. a formed body, it contains the stabiliser composition of one of with good grounds claim 1-3 at least, or according to the stabiliser composition of one of claim 4-8 preparation or according to the polymer composition of one of claim 9 or 10.